Thiophosphoric acid esters



United States Patent 2,995,568 THIOPHOSPHORIC ACID ESTERS Hugo Malz, Leverlmsen, Otto Bayer, Leverkusen-Bayerwerk, and Richard Wegler, Leverkusen, Germany, asslgnors to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany No Drawing. Filed Jan. 19, 1959, Ser. No. 787,333 20 Claims. (Cl. 260-326.5)

The present invention relates to and has as its objects thiophosphoric acid esters and their production. The new compounds of the present invention generally may be represented by the following formula (R0)gP-S,NR,R

in which Rstands for alkyl or aryl radicals, R stands for the radicals 0 o JX, X, ("J0X, iiN(X)2, OEN

wherein X stands for same or dilferent alkyl or arylradicals and R stands for the same or a different radical R, in case of R -SOz-X or for hydrogen, alkyl or aryl radicals; R and R furthermore may form the radical of a cyclic dicarboxylic 7 The symbols in these formulae have the same significance as given above. More specifically R in the above said formulae may be a lower alkyl, cyclo alkyl or phenyl radical, N(R R more specifically may be the radical of a carboxylic acid amide, dicarboxylic acid imide, sulfonic acid amide, disulfonic acid imide, carboxy-sulfonic acid imide, carbodiimide, urea, urethane, hydantoin, amidine, cyanamide, guanidine, and the like.

The above shown reaction is surprising since it was to be expected that N-halo-amides or -imides, being compounds with a positively induced halogen, would have an oxidizing effect on. the thiol group of thiolor dithiophosphoric acid esters which are rather sensitive to oxidation. Thus, dithiophosphoric acid esters of the above mentioned type are, for example, readily converted by into the corresponding disulfides:

free halogen (cf. for example B. Ping-Fang and C. Wan-Yi: Acta In this way, triesters of the general formula 2,995,568- Patented Aug. 8, 1961 chim. sinica 22 1956, page 213 ff.), whilst, on the other hand N-chloro-succinimide easily converts alcohols into the corresponding carbonyl compounds (cf., for example, Houben-Weyl, vol. VII/ 1, page For the reaction according to the invention there are particularly suitable the alkali metal salts of thiolor thiolthiono-phosphoric acid-0.0-diesters which are chiefly V reacted in a finely divided dispersion or solution in inert solvents such as hydrocarbons, halogenated hydrocarbons,

tertiary alcohols or ethers, with the N-halocarboxyor -N-halo-sulfonic-amides or -dicarboxy imides, -carboxy sulfoni-mides, -disulfonimides or -car bodiimides and the like or with solutions thereof in iner-t solvents of the aforesaid type. 1

The 0.0-diesters of thiolor thiolthiono-phosphoric acid to be used as starting materials or their salts as well as the above mentioned N-haloamido or -imido compounds are known by themselves or are easily obtainable by the known methods for preparing the known oompounds. I

'The new phosphoric acid esters are intended to be used as pest control agents as well as in the rubber industry.

The new compounds of the present invention very effectively kill insects like flies, mites, aphids, etc. They distinguish themselves especially by a good contact-insecticidal activity and sometimes by an activity on eating insects such as caterpillars. Most surprisingly they are of remarkably low toxicity against mammals. They may be.

used in the same manner as other known phosphoric insecticides, i.e. in a concentration from about 0.00001% to about 1% diluted or extended with suitable solid or liquid carriers or diluents. Examples of such solid carriers are talc, chalk, bentonite, clay and the like, as liquid carriers there may be mentioned water (if necessary with commercial emulsifiers), alcohols, especially lower alcohols such as methanol or ethanol, ketones, especially lower ketones such as acetone or methyl ethyl ketone, liquid hydrocarbons and the like. The new compounds-may fur- 1 thermore be used in combination with each other or with known insecticides, fefiilizers etc.

As an example for the special utility of the inventive 3 compounds the compounds of the following formulae (0 GEN (B-CsH10)IPS-N a lo-tart.

(C:H50)|P-SN- 0 02116 i have been tested against flies (Drosophila) and spidermites (Tetranychus telarius althae). Aqueous solutions have been prepared by admixing the above shown compounds with thesame amount of an auxiliary solvent (acetone). A commercial emulsifier (benzyl hydroxy diphenyl polyglycol ether) is added in an amount of 20% referred to active ingredient. This premixture then is diluted with water to the desired concentration. The tests have been carried out as follows:

(a) Against flies (Dr0s0phila).-In petri dishes of about 5 inches diameter filter paper has been placed,

which has been wetted with aqueous solutions of the above shown active ingredients I and II prepared as indicated above. About 30 flies have been placed under the covered after 124 hours.

petri dishes .and the living status has been determined The following results were -.ob.tained;

Aqueous concentration Compound (inperoent I Killingzate active (in :percent) ingredieut/ water :0. 2 t 5100 (II) 0.2 300 (b) Against spider mites (T etranychus :telar'ius -.alrhate).--'Bean plants (.Phaseolus vu'lgaris) of about inches height are sprayed drip wet with aqueous solutions of the above shown active ingredients II and 1H prepared as indicated above. The beam plants have been infested heavily with the two-spotted spider (species .Tetranychus telarius). Evaluation has lbeencarried .out after hours, 48 hours and 8 days. The following results have been obtained:

Aqueous concentration Compound (ln percent -Ki11ingrrate active (in percent) ingredient] water) a- 0.2 i '100 iii) 0.12 '100 The compound of the following formula The following examples are given for the purpose of illustrating the invention.

Example 1 (C3H50)2I[;- S C2H5 42 grams (somewhat more than /5 mol) of .the sodium salt of =0.0-diethyl-thiolth-iono-phosphoric acid are suspended in about 500 millilitres of dry benzene. A solution of 24.8 grams /5 'mol) of N-chlorurethane in 150 millilitres of dry benzene is added dropwise with stirring to this suspension. In a moderately exothermic reaction (reaction temperature about 35 C.) the benzeneinsoluble sodium salt of 0 .O-diethyl-thiolthiono-phosphoric acid gradually disappears from the reaction mixture and a finely divided sodium chloride precipitate begins to separate out. The mixture is afterstirred for some time (about 2 hours) and the precipitated common salt is separated 01f. The solvent is removed from the clear filtrate by evaporation under vacuum. A residue of a pale yellow clear'oil is thus obtained which crystallizes after some time. The crystalline product is freed from unerystallized portions by filtering with suction or squeezing dryly and then redissolved from hot light benzene. Colorless crystals of melting point 71-73" C. are thus obtained.

Calculated for C H O NPS C, 30.76%; H, 5.90%; N, 5.13%; P, 11.33%; S, 23.46%. Found: C, 31.17%; H, 5.94%; N, 5.20%; P, 11.3%; S, 243%.

By the same way but using instead of the sodium salt of 0.0-diethyl-thiolthionophosphoric acid the equimolecuphor ic 'acid there :is obtained the tcompoundmf the tin]- lowing ionn ula Example .2

To a suspension of732 grams nf-the sodium sa ltsof' ofO- -diethylethiolthionophosphoiiic' acid .250 millilitres of benzene there isadded :dropwise with stirringv esolution of 22.7 grams of Nechloro-flethylurethane in milli- 'litresof benzene. .A reaetiontternperature of-2543 0 C. is maintained by appropriate cooling'with water. While the sodium salt of the dithioaphosphoriic racidester :slow- 1y disappears from the motion mixture, a-ifinely disperse sodium chloride precipitate iseparatesaout which is 'sep .aratedkofi' after further .stirringxitior about-i1 hour; The clear pale yellow benzene 'solutioniisczonoentrzated under vacuum, until "the solvent is completely removed. clear brownish oil is thus dht-ained as residue which :does not crystallize, even upon prolonged cooling a mixture of ice and :oomrnon :saflt.

Calculated for C l-1 50 10138 C, 35138795; H, 6.69%; N, 4.65%; P, 1 0.28%; S, 21.28%- Found: C, 36.34%; H, 6.31%; N, 4.49%; P, 9.51%; .s, more.

By the same way but insteadof N-ehluro-N- ethylurethane the equimolecular amount of N-chloro-N- phenyl-uret-hane there is obtained the compound ofithe following formula Ida manner correspondingto that described in Example 3, a suspensionof 32 grams of the'pota'ssium-salt of 0.0-diphenyl-thiolthionophosphoric :acidin-SZSI) milli litres of bcnzeneis reactedwith a solution'of 15.2. grams of N-chloro-N-ethylurethane in I100millilitres ot-benzene. After separating off thev precipitated potassium chloride and :removingthe solvent under vacuum, a non crystalliz able'brownish oil is obtainedasresidue.

Calculated for C H QNP'S 0,5137%; 115.07%: N, 3.52%.; P, 7.79%; S, 16.13%. Fonndz'C; 51.28%;11, 535'%';N,.3.60%; P,.'7.65'%',"S, 16.0%.

- 13.4 grams of N-chloro-succinimide.

Example 5 O -CH,

(CgILOhP-S-N g G H:

Into a suspension of 21 grams of the sodium salt of 0.0-diethyl-thiolthiono-phosphoric acid in 300 millilitres of benzene are introduced in small portions with stirring In the. course of the slightly exothermic reaction the chlorimide as well as the sodium dithiophosphate gradually disappear from the reaction mixture and a finely disperse sodium chloride precipitate separates out. In order to complete the reaction, the mixture is heated to about 50 C. for a further /1 hour. The-precipitated sodium chloride is separated off from the cold reaction mixture and the clear colorless benzene solution is concentrated under vacuum, until the solvent is completely removed. A colorless smeary resi-- due is thus obtained which crystallizes after a short time. The crystals are squeezed dryly and recrystallized from hot alcohol. They then show a melting point of 94.5- 96 C.

Calculated for C H O NPS C, 33.92%; H, 4.98%; N, 4.94%; P, 10.93%; S, 22.64%. Found: C, 34.15%; H, 5.37%; N, 5.08%; P, 10.8%; S, 22.35%.

By the same way but using instead of N-chloro-succinimide the equimolecular amount of N-chloro-phthalimide there is obtained the compound of the following formula (M.P. 123 C.)

Example 6 To a suspension of 22 grams of the sodium salt of 0.0-diethyl-thiolthionophosphoric acid in 250 millilitres of benzene there is added dropwise with stirring a solution of 20.6 grams of N-chloro-N-methyl-benzene-sulfonic acidv amide in 100 millilitres of benzene. The reaction proceeds similarly to that described in Examples 1 to 5. In order to complete the slightly exothermic reaction, the mixture is after-stirred at 45-50 C. for A hour. The

precipitated sodium chlorideis separated off from the reaction mixture and the benzene solution concentrated under vacuum. After complete removal of the solvent,

By the same way but using instead of N-chloro-N- methyl-benzene-sulfonic acid amide the equimolecular amount of N-chloro-N-methyl-methane sulfonic acid N, 3.10%; P, 6.86%; s, 21.31%.

6 amide there is obtained the compound of the following formula In a similar manner to that described in Example 6 a suspension of 32 grams of the potassium salt of 0.0-diphenyl-thiolthiono-phosphoric acid in 300 millilitres of benzene are reacted with a solution of 20.6 grams of N- chloro-N-methylbenzene-sulfonic acid amide in 150 millilitres of benzene. Upon concentration of the benzene solution freed from the precipitated potassium chloride, under vacuum, a light brown oil remains behind which crystallizes on rubbing with methanol. After squeezing dryly, the colorless crystals are de-dissolved from hot methanol. M.P. 92-94" C.

Calculated for C19H1304NPS3i C, H, Found: C, 50.52%;

t H, 4.01%; N, 3.18%; P, 6.9%; S, 21.8%.

In the manner described in Example 1, a suspension of 22.4 grams of the potassium salt of 0.0-diethyl-thio1- thionophosphoric acid in 250 millilitres of dry benzene is reactedwith a solution of 16.9 grams of N-chloroacetanilide in millilitres of benzene. After separating off the potassium chloride formed in the course of the reaction, the clear filtrate is concentrated under vacuum.

Upon cooling, the residual light brown oil solidifies to form a crystalline mass which, after re-crystallization from petroleum ether, shows a melting point of 60-62 C.

Calculated for C H O NPS C, 45.13%; H, 5.68%; N, 4.38%; P, 9.7%; S, 20.08%. Found: C, 46.0%; H, 5.97%; N, 4.4%; P, 9.9%; S, 19.3%.

By the same way but using instead of N-chloro-acetanilide the equimolecular amount of N-chloro-N-methylbenzamide there is obtained the compound of the follow- Example 10 (CH:O)zI"-S N--C-O CsHs 17 grams of the sodium salt of 0.0-dimethyl-thiolphosphoric acid are suspended in 250 millilitres of benzene. To this suspension there is added. dropwisea-with'; stirring a solution of 13.7 grams of: N-chl'oroll-methyl?- urethane in 50 millilitres of benzene. The temperature. of thereaction mixture rises. thereby gradually to about: 30 0, Whilst the sodium-thiolphosphate; completely dis-' solves. In order to complete thereaction, the'mixturc I is after-stirred at 4050 C. for about 1 hour. The1prercipitated sodium chloride is filtered ofi withsuctionzfrom. the cold. reaction mixture and the filtrate 'concenttatedby evaporation under vacuum. A colorless to. pal'ezyellow' oil is thus obtained which is first freed fronrsmallportionss of insoluble impurities by means ofv a-glass suctionefilter (CH OhP-S-N COCH2 A suspension of 17 grams of the'sodiurn salt'0f"0.0I.- dimethyl-thiol-phosphoric; acid is reacted with. 13. grams of N-chloro-succinimide as described in Example 5.. Upon working up the reaction product, a-pale yellow oil is obtained which crystallizes after a short tirne; The: crystal slurry is taken up in hot'benzene. The hotsolue tion is treated with an amount of benzene so thata permanent cloudiness just occurs. Upon cooling the-so'flution, a colorless substance crystallizes with ameltingv point of 9093 C.

Calculated: C H O NPS. C, 30.13%;H, 412l%-;;N, 5.86%; P, 12.95%; S, 13.40%. Found: C, ;65%;'H;. 4.20%; N, 6.01%; P, 12.4%; S; 12.7%.

By the same way but using instead-of N-chloro=succinimide the equimolecular amount of N-chloro-saccharine" and then fractionated under-vacuum.producedby arr-oil;

(N-chloro-sulfobenzoic acid'imide) there is obtainedthe:

compound of the following formula" Example 12 Example. 15;

(C2HsO)zP--SN-(?H l A suspension of 22.4 grams of the potassium saltiof 0.0diethyl+thiolthionmphospliorici: acidfiir 25a millilitres of). b'enzeneris'i-a reacteds with. at solution. of? 1555.. grams. of N chlora-formanilidein. 150.:millilitre's-of bennne. as de scrib'edi in Example 8; Upomworkingmp; .anzoil? residueis' obtained: which; crystallizes;- on: standing; After"- re-- crystallization from. ethanol,v thercrystals:shovwatmeltingz Found": C, 43.36% 522. NA-593% R 1'01Z%';;S;. 21.6%

Weclaim: 1.1. The phosphoriaacid':esten-ofthe following formulav (oiHto),1 i "-s-NH1- -ocm 42 The phosphoric acid? esterzoff theafollowingiormula.

(CzH;0)lPs'-Nic-oolmi- The: phosphoric: acid? ester: of the: following formula.

63-. The: phosphoric: acidLesteirs-of i the'fol-lowin'g; formula- (c11r50 ms -iI'SOz-.

: on. T1. The; phosphoric; acid; ester. ofi. the? following: formula. oiH50 ,1 -s-1 I's0,. -c1 0H5. 8'. Thea phosphoric:acidiiester of? the." following; formula iEiQ)zfiC 5 9.1: The: phosphoricracidiesten offtheiollowingformula 10'; Tlies'pliosph'or'iczacidiester ofitlie"followingxfbnnula 117 TIiezpliospl ioiCcacidiester ofitliesfollowinggformulaa 122... 'lllieepl'iosghoric':acidiestenofi'therfollowingionnula.

159: The -pliosghoficracidlester:oftlimfollowingfbnnula.

14. A phosphoric acid ester of the following formula in which Y is a chalcogen having an atomic weight from 16 to 33; R is a member selected from the group consisting of lower alkyl and phenyl radicals; R is a member selected from the group consisting of lower alkyl carbonyLphenyl carbonyl, tolyl carbonyl, chlorophenyl carbonyl, lower alkoxy carbonyl, lower alkyl sulfonyl, phenyl sulfonyl, chlorophenyl sulfonyl, and cyano; R is a member selected from the group consisting of hydrogen, (CH ),,H, wherein n is a whole number from 0 to 10, phenyl and a group as R and R and R taken together with N is a radical selected from the group consisting of succinimido, phthalimido and sulfobenzimido.

15. -A compound of claim 14 wherein R is lower alkyl,

R is lower alkoxy carbonyl and R, is -(CH ),,H wherein n is a whole number from 0 to l0.

16. A compound of claim 14 wherein R is lower alkyl;

R is lower alkyl carbonyl and R is phenyl.

17. A compound of claim 14 wherein R is lower alkyl,

. R .is cyano, and R, is -(CH H wherein n is a whole R is phenyl carbonyl, and R is --(CH I-l wherein nis a whole number from 0 to 10.

References Cited in the file of this patent UNITED STATES PATENTS 20 2,891,059 Malz emu"--. June 16, 1959 

14. A PHOSPHORIC ACID ESTER OF THE FOLLOWING FORMULA 